Chemical School of Zhang Dayu State Key Laboratory of Fine Chemicals , Dalian University of Technology , Dalian 116024 , China.
Collaborative Innovation Center of Chemical Science and Engineering , Tianjin 300071 , China.
ACS Appl Mater Interfaces. 2018 Apr 25;10(16):13462-13469. doi: 10.1021/acsami.8b00350. Epub 2018 Apr 12.
Dehydrogenation of the tetrahydroisoquinoline derivatives coupled with hydrogen production is important for hydrogen storage applications. Herein, we formulated a new system that embedded Dawson-type polyoxometalates as efficient photosensitizers into the pores of redox-active coordination polymers for the light-driven photocatalytic oxidative Mannich reaction and hydrogen evolution. In the designed Co-POM polymer, UV light excitation gives the excited state of the Dawson-type polyoxometalate first to oxidize electron donors or substrates; the reduced form (i.e., heteropolyblue) adsorbs visible light to achieve a new excited state, which reduced the cobalt redox sites and facilitates hydrogen evolution reaction. The photosensitizer recovered to the ground state, completing the catalytic cycle. Under the optimized conditions, Co-POM enabled the hydrogen evolution and dehydrogenation of tetrahydroisoquinoline without the presence of any other additives. The high catalytic efficiency and robustness indicated the advantages of the combining functional polyoxometalate-based catalysts and porous characters of the coordination polymers for the development of highly active heterogeneous catalysts.
四氢异喹啉衍生物的脱氢与产氢对于储氢应用非常重要。在此，我们构建了一个新体系，将 Dawson 型多金属氧酸盐作为高效光敏剂嵌入到氧化还原活性配位聚合物的孔道中，用于光驱动光催化氧化曼尼希反应和产氢。在所设计的 Co-POM 聚合物中，紫外光激发首先使 Dawson 型多金属氧酸盐处于激发态，以氧化电子供体或底物；还原形式（即杂多蓝）吸收可见光以达到新的激发态，从而还原钴氧化还原位点并促进产氢反应。光敏剂恢复到基态，完成催化循环。在优化条件下，Co-POM 能够在没有任何其他添加剂的情况下促进四氢异喹啉的脱氢和产氢。高催化效率和稳健性表明，将基于功能化多金属氧酸盐的催化剂与配位聚合物的多孔特性相结合，对于开发高活性多相催化剂具有优势。
